Photographic elements having an anchoring substratum composed of a water-insoluble vinylpyridine polymer



Aug- 12, 1952 F P. ALLES ET AL 2,606,832

PHOTOGRAPHIC ELEMNTS HAVING AN ANCHORING SUBSTRATUM COMPOSED OF A WATER-INSOLUBLE VINYLPYRIDINE POLYMER Filed NOV. 27, 1946 HYnRoLYzED ETHYLENE/ vINYI. ACETATE COPOLYMER- sILvER I-IALIDE I HYDRoLYzEo ETHYLENE/VINYL ACETATE COPOLYMER PoLYvINYLPYRIDINE F l G 1 cELLuLosI-z NITRATE HYDROLYZED ETHYLENE/VINYL ACETATE COPOLYMER SILVER HALIDE CELLULOSE NITRATE o-suLFoBENzALDEHYDE PoLYvINYLAcI-:TAL-SILvI-:R HALIDE HYDRoLYzeD ETI-IYLENE/VINYI. ACETATE COPOLYMER PoLYvINYL PYRIDINE F| Q 4. cELLuLosE NITRATE GELATIN SILVER HALIDE GELATIN METHYL METHACRYLATE/ Z-VINYLPYRIDINE COPOLYMER f4 PoLYvINYLcHLoRIDE FI G. 5

2, HYDRoLYzED I-:TI-IYLENE/ VINYL ACETATE COPOLYMER- SILVER HALIDE POLYVINYL ALCOHOL- BORIC ACID 9 le PoLYvINYI. PYRIDINE FI G 6 POLYVINYL CHLORIDE 25 HYDROLYZED ETHYLENE VINYL ACETATE COPOLYMER- 24 SII-VER HAI-DE lilla/Miramar; HYDROLYZED ETHYLENE/VINYL ACETATE COPOLYMER 22 5ETHYL2VINYLPYRIDINE POLYMER F| Q 7 cI-:LLuLosE NITRATE 25 {HYDROLYZED ETHYLENE/VINYL ACETATE COPOLYMER- 24 W 1 z m g SILVER HALIDE HYDROLYZED ETHYLENE/VINYL ACETATE COPOLYMER VINYLPYRIDINE/METHYL METHACRYLATE COPOLYMER CELLULOSE NITRATE HYDROLYZED ETHYLENE/VINYL ACETATE COPOLYMER- SILVER HALIDE HYDROLYZED ETHYLENE/VINYL ACETATE COPOLYMER VINYLPYRIDINE/STYRENE COPOLYMER CELLULOSE NITRATE INVENTORS.'

FRANC/S PETER ALLES Y WILL/AM RUSSELL SANER A TTORNEY.

Patented Aug. 12, 1952 PHOTOGRAPHIC ELEMENTS HAVING AN ANCHORING SUBSTRATUM COMPOSED F A WATER-INSOLUBLE VINYLPYRI- DINE POLYMER Francis Peter Alles and William .Russell Saner,

North Plainfield, N. J., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a

corporation of Delaware Application November 27, 1946, serial No. 712,742

This invention relates to photographic elements, and more particularly, to such elements which have a novel and improved substratum layer for anchoring water-permeable colloid layers to the support,

An object of this inventiony is to'provide new and improved photographic elements. A further Objectis to provide photographic elements with improved anchoring substratum layers. A related object is to provide photographicflm elements with hydrophilic collod layers which adhere strongly to the support by means of an irnproved anchoring substratum. Another object isto provide a simplev and effective method and pyridine coating solution. It is also advantageous tcadd a small amount of an acid to the aqueous coating solutions used to deposita hydrophilic colloid or other layer on the vinylpyridine polymer layer. The acid causes the solution to etch or bite the surface of the said polymer layer and improves thevadherence between the layers.

It has been found that the vinylpyridinepolymer'laye'rs are clear and have excellent adhesion Vto hydrophobic materials in general and to h ydrophilic collod silver halide emulsion layers. The vinylpyridine polymer layers do not have any deleterious effect on the light-sensitivity or stability of silver halide emulsion layers which is advantageous.

The vinylpyridine polymers can be made by polymerizing a monomeric vinylpyridine, e; g.,

8 Claims. (Cl. 95%8) alpha, beta-, or gamma-vinylpyridine or a homologue thereof containing an alkyl radical of one to four carbon atoms in the pyridine ring, in a liquid medium by the aid ofa polymerization catalyst. An organic solvent solution can be used if desired in which. case inert organic solvents are'Y used. However, emulsion polymerization is quiteuseful land bulk polymerization methods Aare effective., The polymerization is preferably carried out in an aqueous mineral acid solution ormedium in the presence of a peroxy compound Vcatalyst at temperatures from Yabout 20 to 50 Cxfcraperiodoften or less toj2'00 or. more hours. The proportionof mineral acid,

means for anchoring water-permeable colloid e. g., hydrochloric'or sulfuric, may vary overa layers to water-insensitive Vor hydrophobic vsupfairly `wide range, e. g., from 0.5 to 2 .5 molsof ports. Still other objects will vbe apparent from acid per mol of -vin'ylpyridine monomer. The rethe following description of the invention. sulting solution may be diluted with water and The above objects are-attained and new .and the solution addedto a basic so1utione.A g., useful photographic elements provided by the aqueous sodium hydroxide, and the precipitated present invention. The elements consist` o f `a resin filtered. washed, and dried. A neutralizing support having on at least one surface of the agent can be present inthe wash water. support an anchoring substratum composed of In making the copolymers, there may beused a Water-inSOlUble Vinylpyidine DOiYmel and@ suchfmaterials as methyl or ethyl acrylates'; hydrophilic collod layer on at least one offfthe methyl, ethyl, isobutyl, and methoxyethyl methsaid polymer layers. The collod layers may supacrylates; methacrylamide and N-methylacrylport still other layers. Y amide; acrylonitrile and methacrylonitrile; sty- The novel elements can be made by Coating rene; vinyl naphthalene, and the like or mixtures a support, s uch as a cellulose derivative, superof two or more of these cmpounds, 11013711161. e. ge nYlOn, polyvinyl Chloride, POly- Inapreferred aspect of the invention, the polyethylene, glass, Water-DTOOfed Paper etc" With mers of unsubstituted alpha-or 2-vinylpyridine or a solution of a water-insoluble vinylpyridine its inter-polymers containing 1 to 20% 0f a difpolymer t0 form a thin layer' A 50111151011 emul" ferent interpolymerizable monomer are used. sion, ordispersion of a hydrophiliccolloid is then 'Such polymers are non water so1ub1e synthetic coated onto the dried vinylpyridine polymer layer. resins somb1e'ina1c0ho1s,' e@ g., methyl, ethyl, A'fdltlona layers may then be coated on the co1' propyl, and butyl, and mixtures of such alcohols lold 1 ayersf with ketones, e. g., acetone, methyl ethyl ketone, I t lsenerapy advantageous t2 ,usef Solvent methyl propyl'ketone, and methyl isobutyl ketone Whmh'ls Volatlle and softens or .bn-els bfhqsur' or in certain chlorinated hydrocarbons, e. g., -triface of the support .for the water-mso u e vinyl- 40 -Chlorethylenek A practical method of forming the novel anchoring substratum is as follows: The particular vinylpyridine polymer "is dissolved in a water-miscible alcohol, preferably methanol or ethanol, in an amount of 0.25% to 20% by weight of the alcohol. The solution is thenapplied to or coated onto a surface ofthe support by any of the conventional methods used in making photographic elements. Thus the solutions can be applied from a hopper provided with av doctor blade, dipping, by transfer or beading rollers, lor spraying and the solvent removed by allowing Vit to evaporate,"drying, etc.

In the accompanying drawing which constitutes partof this specification:

Fig. 1 is an enlarged section lof the film element described in Example I,

Fig. 2 is an enlarged section ment described in Example II, Fig. 3 is an enlarged section ment described in Example IV,

Fig. 4 is an enlarged section ment described in Example V,

Fig. 5 is an enlarged section ment described in Example VI,

Fig. 6 is an enlarged section of the film ment described in Example VII.

Fig. 7 is an enlarged section oftheiilm ment described in Example VIII,

Fig. 8 is an enlarged section of the iilm ment described in Example IX,

Fig. 9 is an enlarged section of the film ment described in Example X.

The invention will be further illustrated but is not intended to be limited by the following examples. The parts areby weight and the vinylpyridine polymer made by polymerizing unsubstituted Z-vinylpyridine.

EXAMPLE I A 4% solution of polyvinylpyridine in methanol/ethanol (5S/40 by weight) is applied to a cellulose nitrate base I and the resulting layer 2 isv dried for about two minutes at about 60 C. A 3% solutionY of acompletely hydrolyzed ethylene/vinyl acetate copolymer of the kind described in United States Patent 2,397,866 in ethanol-water (2:7 ratio)V containing 1 cc. of glacial acetic acid per 100 cc. of solution is coated onto the polyvinylpyridine layer. A hydrolyzed ethylene/vinyl acetate copolymer silver halide emulsion of the type-described in said patent. is coated over Vthe clear hydrolyzed ethylene/vinyl acetate layer 3 and resulting-emulsion layer 4 is Vdriedat about 60 C. The resulting iilm element has excellent wet and dry anchorage. The silver halide emulsionlayer evidenced Yno tendency-to separate during development in a standard hydroquinone metol developing solution nor during fixing in a sodium thiosulfateY bath containing approximately 1% of acetic acid.

EXAMPLE II A 3% solution of polyvinylpyridine in methanol is applied to a cellulose nitrate base I and the resulting layer 2 is dried for about two minutes at about 60 C. A 3% solution of a completely hydrolyzed ethylene/vinyl acetate copolymer in ethanol/water (2:7 ratio) containing 1 cc. of concentrated acetic acid per 110 cc. of said solution is coated onto the polyvinylpyridine-layer. A dispersion of colloidal silver in a similar 3% solution of said copolymer free from acid is coated onto the copolymer layer 3. Vcellent anchorage to each other and to the support.

A silver halide emulsion layer 4 of the kind described in Example I can be coated .onto the colloidal silver layer 5, if desired, and additional emulsion layers coated in like manner.

EXAMPLE III A 3% Vsolution of polyvinylpyridine in a mixture of acetone and methanol having a ratio of 11 to 2 by volume is coated onto a. cellulose acetate film and dried two minutes at 60 C. A solution of a completely hydrolyzed ethylene/vinyl acetate copolymer containing 1 cc. of concentrated acetic acid per 110 cc. of solution is coated onto the polyvinylpyridine layer. persion of the kind described in Example II is coated onto the clear layer of copolymer and of the film eleof` the iilm cleof the fum eieof-theiilm eleeleele-

ele-

ele-

A colloidal silver dis- 4 dried. The layers have excellent wetand dry adherence. 'y

Silver halideemulsion layers can be coated onto the layer of colloidal silver. A layer of polyvinylpyridine can be coated on the other surface ofthe film in like manner and a lightsensitive silvenhalide emulsion coated thereon as The layers have exdescribed in Example I.

EXAMPLE IV A.-3% 'solution of polyvinylpyridine in a mixture of acetone and methanol having a ratio of 11 to -2 by volume is coated onto a cellulose acetate film 6 and dried two minutes at 60 C. A gelatin solution of the following composition:

. Per cent Gelatin 2 Aceticgacid (glacial) ,.e", 1 Methanol ,Y. ,87 Water V V 10 EXAMPLE V A 3% solution of polyvinylpyridine in methanol is applied to a cellulose nitrate base I0 and 'the resulting layer I l is dried for about two minutes at about C. A 3% solution of a completely hydrolyzed ethylene/vinyl acetate copolymer of thekind described in United States Patent 2,397,866 in ethanol-water (2:7 ratio) containingV 1 cc. of glacial acetic acid per 100 cc. of solution is coated onto the polyvinylpyridine layer; A light-sensitive silver halide emulsion is made by precipitating silver halidesin an orthosulfobenzaldehyde acetal of polyvinyl alcohol in a manner similar to that described in Exn ample I of United States Patent 2,397,866. The emulsion layer I3 and intermediate layer I2 of hydrolyzed ethylene/vinyl acetate copolymer had excellentadherenceto the base byvvirtue o f the anchoring substratum of polyvinylpyridine.

EXAMPLE VI A polyvinylchloride iilm base I4 -is 'coatedwith a thin substratum I5 'from a solution of a Waterinsoluble methyl methacrylate-Z-Vinylpyridine copolymer in trichlorethylene. An aqueous. solution containing 2% of gelatin and 5%v of glacial acetic acid by Weight is coated onto the copoly- 'mer and dried; A gelatino-silver halide emulsion is coated onto the gelatin substratum I6 forming emulsion layer I'I. The resulting hlm exhibits good anchorage between the coated layers.

EXAMPLE VII A polyvinylchloride lm base` I8 was coated with a 6% solution of polyvinylpyridine in equal parts of trichlorethylene and methanol. A thin layer` 2D of polyvinyl alcohol containing 'boric acid iscoated onto the resulting polyvinylpyridine layer I9- and a silver halide emulsion of the typedescribed in Example I is coated onto the polyvinyl alcohol layer to form emulsionlayer 2 I. The layers had good wet and dry anchorage.

EXAMPLE VIII v A solution of 5-ethyl-2-vinylpyridine polymer containing three parts of the polymer in 57 `parts of ethanol and "lv 'parts ofacetone is applied to a'.vr cellulose nitrate base 22fa`nd the resulting layer 23 is dried for about two minutes at about 60v C. A 3%"solution ofv'a'completelylhydrolyzed ethylene/vinyl acetate copolymer ofthe kind described in United Statesv Patent 2,397,866? in 4ethanol-- vwater (50 parts to AiT'lp'artsrby* weight) containing 5 cc. of glacial'actic acid Iper-rlOO-cciof solution is coated on 'the 5-ethy1-'2-vinylpyridine Vpolymer layer andfdried at about60 C. A hydrolyzed ethylene/vinyl acetate copolymer silver halide emulsion layer 25 oflthe' type described above? is coated over 'the clear'hydrolyzed ethylene/vinyl acetate layer 24` and dried at about 60 C. The resulting'lin element has satisfactory wet and dry anchorage after processing.

Forv vthe `5-ethyl-2-vinylpyridine polymer Asolution used in .Example .VIII .is substituted agsolution" .of vinylpyridine/methyl methacrylate copolymerl (80/20 by'weight) containingthree parts of `the polymer in. 57 -parts ofethanol and 40 parts of acetone. The resulting'lmlelementhas satisfactory Wet and dry anchoragefafter processing.V This .lm element is shown in.Fig.8 of

the drawing and consists-of cellulose nitrate film .base 22 having fsuperposedi thereon in ordera lvinylpyridine/In'ethyl methacrylate kcopolymer lay-er 23', hydrolyzed ethylene/vinyl lacetate'copolymer layerV 24 and vhydrolyzedethylene/viny acetate copolymer-'silver emulsion layer 25.

EXAMPLXf Y Y For the 5'4- ethyl-.2-vinylpyridine ,polymer solultion' used in Example VIII is'substituted asolu- -tion io'f vinylpyridine/styreneV copolymer (80/ 20 by Weight)` containing three vpartsof the polymer in 57 parts "of ethanoll and 40 parts of acetone. The resulting film element has satisfactory Wet and dry anchorage after processing. This nlm element is shown in Fig. 9 of the drawing andconsists of cellulosejnitrate lm base 22 having superposed thereon in order a vinylpyridine/styrene vcc'npolyi'nerfla'yer 23, hydrolyzed ethylene/vinyl acetate copolymer layer 24 and hydrolyzed ethylene/vinyl acetatey copolymersilver halide emulsion layer 25.y

'A ,3% jsolution of poly-2-vinylpyridineV in methanol/ethanol (1:1 by weight) is applied/to :a cellulose nitrate base andtheresulting layer isLdried-for'two 4minutesat aboutV 60 C. A hydrolyzed ethylene/vinyl acetatefcopolymer silver vhalide emulsion of the type described inUnited vStates Patent 2,397,866 containing-1 cc.,of glacial Procedure A 240 cc. 0.5N aqueous KI 1680 cc. Water B 1390 cc. 3N AgNOs 825 cc. 11.6N NHiOH 1680 cc. Water 4800 g. of Ya,10% aqueous solutionof a hydrolyzed mint'erpolyrn'er of ethylene/vinyl acetate con taining 5% `by Weight of ethylene 1465 cc. 3N ammonium'bromide 1200 cc. water A 25.0. ccfN-AgNOa Y 150.cc.120% NH4OH 200cm-,Water Y' 255 ccjaN' N'HiBr cc.Water f y 25- g. hydrolyzed *ethylene/vinyl actate `copolymer of procedure-A y 'fl j-.

100 cc. glacial acetic acid 275 g. hydrolyzed ethylene/vinyl acetate copolymer of procedureA B is brought to 112 F. and A added at 95 F. in v30 seconds. The mixtureis stirred one minute and then C is added at room temprature. 'I'he mixture is then, cooled to 100 F. and D is'added at F. in 30 seconds. The emulsion is then chilled, Washed, etc. in a conventional manner. Various radiation-sensitive 'materials maybe present in the layers coated ont'o the anchoring substrata.' In addition tolight-sensitive silver salts, su'ch as silver chloride, silverbromide, silver-.chloride-bromide.' silver-chloride-iodide and .similar mixtures, Vthere may be utilized `4bichromated hydrophilic colloids, e. g., albumin-gelatin, gum arabic, polyvinyl' alcohols, or gluell Im'- lmobile color formers, dye intermediates-101 dyes may be present in'such layers. Otherl'materials 'include light-sensitive iron salts 'and' diazonium compounds wither without coupling components. .With certain of i these `light-sensitive materials, egg., the diazo compounds; thebinding agent-may have a low sensitivity to water. Thus, polyvinyl acetate ora cellulose acetate may be-use'd as'ithe colloidal binder. i

The invention is not limited to the use of the specific lm bases described in the examples but may be used with practically any transparent film. The polyvinylpyridine layers are adherent to various other nlm materials, e. g., polyamides, cellulose nitrate, polyvinyl acetals, cellulose propionate, cellulose mixed esters, cellulose ethers, vinyl chloride copolymers, styrene, acrylonitrile copolymers, polyesters, vinyl acetate copolymers, vinyl fluoride copolymers, polyvinyl alcohol, transparentized paper, etc.

These substrata are not necessarily used alone to join the support and light-sensitive layer but may, if desired, be used in conjunction with other substratum layers, such as gelatin, water-sensitive cellulose esters, Water-proofing layers, and lter layers. Also, it is possible to incorporate removable or bleachablesilver and antihalation dyes in these layers.

The vinylpyridine polymer layer being an acid acceptor will screen out acidic decomposition products produced by thebase material and thus protect the superimposed sensitized layer from the deleterious effects of such acid decomposition products.

The products of this invention have Wide application in the general iield of photography depending upon the type of water-permeable colloid layers attached to the support. When lightsensitive silver halide dispersions inwater-permeable binders are employed, these elements are useful in producing the common photographic negatives and cine positives. The lms are also useful in producing matrices for printing or dye transfers and for use in the graphic arts in general. Color films using these substrata are especially useful since the substrata contain no migratory or volatile acidic compounds which can cause fading of the colors. The products also have utility in fields outside of photography, e. g., in special adhesive uses and in the treatment of textiles.

As many Widely diierent embodiments of this invention can be made Without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims.

What is claimed is;

l. A laminated photographic element comprising a support, a Water-permeable organic colloid layer anchored to a surface of the support by means of an intercalated layer composed of a Water-insoluble vinylpyridine polymer which is solublefin methanol and ethanol and mixturesv of such solvents and forms clear resin ilms, said elementzhaving a layer of alight-sensitive silver halide emulsion..

ylms, said element having a layer of a light-sensitive silver halide emulsion.

3; .A`v laminated photographic element compris- .ingga support, a Water-permeable organic colloid layer-1` anchored to a surface of the support by means of'an intercalated layercomposed of a water-insoluble poly-Z-vinylpyridine polymer which isV soluble in methanol and ethanol and 4mixtures of such solvents and forms clear resin films, said element having a layer of a light-sensitive silver halide emulsion.

4. A laminated` photographic.- elementcompris,.- ing a Water,--insensitive,filmsupport,v a Water-permeable colloid layer anchored to asurface ofthe support by -meansof an intercalated layer composed of a; water-insoluble poly-2 -vinylpyridine polymer which Yissoluble iii-methanol and ethanol and mixture ofV such solvents and forms-clear resin films, said element having-a'layer of alightsensitive silver `halidegemulsion.l i

5. A laminatedrphotographic element comprising a support, aV water-permeable colloid-silver halide emulsion layer anchored to asurface of the support by kmeans of an4 intercalatedlayer composed of a water-insoluble,v-inylpyridine polymer which is soluble in methanol and4 ethanol and mixtures of such solvents and-formsclear resin 6. A laminated photographic element comprising a Water-insensitive film support, a Water-permeable colloid silver halide emulsion layer'anchored to a surface of the support by meansofL an intercalated layer composed of a water-insoluble vinylpyridine polymer which is solublein meth` anol and ethanol and mixtures of such solvents and forms clear resin lms.

7. A photographic element comprising a waterinsensitive cellulose derivative lm base, a lightsensitive, gelatine silver halide emulsion layer anchored to a surface ofthe film base by means of an intercalated layer-composed of a water-insoluble vinylpyridine polymer which is soluble in methanol and ethanol and mixtures of such solvents and forms clear resin lms.

8. A photographic element comprising a Waterinsensitive cellulose derivative lm base, a lightsensitive, gelatino silver halide emulsion layer an, chored to a surface of the nlm base by meansof an intercalated layer composed of a Water-insoluble poly-2-vinylpyridine polymer which is soluble in methanol and ethanol and mixtures of such solvents and forms clear resin lms.

FRANCIS PETER ALL' ES. WILLIAM RUSSELL SAN ER.

REFERENCES CITED The following references are of record in the le ofthis patent:

UNITED STATES PATENTS Number Name Date 1,627,935. Stincheld May 10, 1927 2,133,110 Nadeau Oct. 11, 1938 2,397,865 Jennings Apr. 2, 1946 2,400,989 Hart et al May 28, 1946 2,448,507 Alles Sept. 7, 1948 2,448,542 McQueen et al Sept. 7, 1948 2.448.552 Schulze Sept. 7, 1948 

1. A LAMINATED PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT, A WATER-PERMEABLE ORGANIC COLLOID LAYER ANCHORED TO A SURFACE OF THE SUPPORT BY MEANS OF AN INTERCALATED LAYER COMPOSED OF A WATER-INSOLUBLE VINYLPYRIDINE POLYMER WHICH IS SOLUBLE IN METHANOL AND ETHANOL AND MIXTURES OF SUCH SOLVENTS AND FORMS CLEAR RESIN FILMS, SAID ELEMENT HAVING A LAYER OF A LIGHT-SENSITIVE SILVER HALIDE EMULSION. 